Abstract
[CoL]+ and [CoL2]+ (L=pyrrole, furan, thiophene and selenophene) were generated in a prototype Nicolet-FTMS 1000 Fourier transform mass spectrometer, where they were irradiated with light from a 2.5 kW Xe arc lamp. Photodissociation thresholds, obtained using energy cut-off filters, yielded the bond energies D0(Co+−pyrrole)=59±3 kcal mol-1, D0(Co+−furan)=57±3 kcal mol-1, D0(Co+−thiophene)=61±3 kcal mol-1 and D0(Co+−selenophene)=64±3 kcal mol-1 (1 kcal=4.184 kJ), as well as D0([Co(pyrrole)]+−pyrrole)⩽48±3 kcal mol-1, D0([Co(furan)]+−furan)⩽46±3 kcal mol-1, D0([Co(thiophene)]+−thiophene)⩽49±3 kcal mol-1 and D0([Co(selenophene)]+−selenophene)⩽51±3 kcal mol-1. The photoappearance threshold for [CoC3H4]+, the CO loss product ion from [Co(furan)]+, yielded D0(Co+−C3H4)=either 33±6 or 32±6 kcal mol-1, depending on whether C3H4 was allene or propyne, respectively. Where possible, these bond energy measurements were further corroborated by ligand displacement reactions and competitive collision-induced dissociation experiments.
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